Concentration and fraction distribution of organics and heavy metals in municipal sludge treated by modified phosphogypsum and acetic acid (signed as MPG/HAC) were studied. The results showed that MPG/HAC conditioning significantly produce synergistic enhancement effect to dissolution of unstable heavy metals wrapped in the stable colloid network. Simultaneously, after conditioning, about 45.16% of organics such as proteins, polysaccharides and humic acid in supernatant was degraded, thus dissociating large amount of active group which accelerated immobilization of dissolved heavy metals and weaken its toxicity. In addition, MPG with a porous structure could adsorb unstable heavy metals and transform them into residual fraction, leading to a considerable decrease in their mobility risk level. Besides, linear regression models showed that a strong oxidizability of sludge, and destruction of colloidal network could greatly promote dissolution of unstable heavy metals. Simultaneously, sludge oxidizability and organics degradation rate, and disintegration of extracellular polymeric substances (EPS) layer highly accelerate immobilization of unstable metals. Excepting Cd, environmental risk of Cr, Cu, Pb, Zn, Ni and As can be effectively weakened after conditioning. Additionally, MPG/HAC conditioning might be appropriate for stabilization of Cd, Cr and Zn in water supply sludge, especially for Zn.